CN110016134B

CN110016134B - Lasting uvioresistant polyamide elastomer and preparation method thereof

Info

Publication number: CN110016134B
Application number: CN201910202994.8A
Authority: CN
Inventors: 冯新星; 梁高勇; 潘凯
Original assignee: Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
Current assignee: Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2021-08-03
Anticipated expiration: 2039-03-18
Also published as: CN110016134A

Abstract

The invention discloses a durable uvioresistant polyamide elastomer and a preparation method thereof. The preparation method comprises the following steps: mixing long carbon chain polyamide salt, an anti-ultraviolet agent, an antioxidant, a catalyst, water, polyether and/or polyester, heating to 170-190 ℃, boosting the pressure to 0.9-1.5 MPa, maintaining the pressure, and simultaneously heating to 200-220 ℃; after the pressure is relieved to normal pressure, heating to 230-260 ℃; vacuumizing, filling nitrogen, discharging and slicing. The anti-ultraviolet polyamide elastomer provided by the invention has excellent anti-ultraviolet performance due to the participation of active functional groups contained in the anti-ultraviolet agent in polymerization reaction, has low cost of preparation raw materials, is harmless to the environment and good in rebound resilience, and can be applied to the fields of high-grade sports equipment, medical materials, special anti-ultraviolet materials and the like.

Description

Lasting uvioresistant polyamide elastomer and preparation method thereof

Technical Field

The invention relates to a lasting uvioresistant polyamide elastomer and a preparation method thereof, belonging to the field of high polymer copolymerization synthesis.

Background

The thermoplastic elastomer includes polyolefins, polyurethanes, polyesters, polyamides, polystyrenes, polyvinyl chlorides and the like, wherein the heat resistance of the polyurethanes, polyesters and polyamides is optimal. The polyamide elastomer has high strength, high toughness, low specific gravity, good bending fatigue resistance, good wear resistance and good low-temperature performance, and can be widely used in the aspects of automobiles, sports goods, medical appliances, sealing elements, mechanical parts and the like.

At present, although some progress is made in the preparation research work of polyamide elastomers, there is still much room for improvement in performance research, for example, materials are prone to aging and degradation when exposed to strong ultraviolet radiation, and research on ultraviolet-resistant polyamide elastomer materials is necessary to solve the problem of ultraviolet resistance. The common ultraviolet-resistant method for synthesizing high molecular materials is a method of adding an ultraviolet-resistant agent in a blending manner or a method of indicating a coating, and has the problems of easy precipitation, easy falling, non-durable ultraviolet resistance and the like.

Disclosure of Invention

The invention aims to provide a lasting uvioresistant polyamide elastomer and a preparation method thereof, wherein the polyamide elastomer has the advantages of good uvioresistant property, lasting uvioresistant performance, low water absorption, good elasticity and high strength, and can be applied to the fields of outdoor sports equipment, medical materials, military materials and the like.

The preparation method of the ultraviolet-resistant polyamide elastomer provided by the invention comprises the following steps:

mixing long carbon chain polyamide salt, an anti-ultraviolet agent, an antioxidant, a catalyst, water, polyether and/or polyester, heating to 170-190 ℃, boosting the pressure to 0.9-1.5 MPa, maintaining the pressure, and raising the temperature to 200-220 ℃ while boosting the pressure; after the pressure is relieved to normal pressure, heating to 230-260 ℃; vacuumizing, filling nitrogen, discharging and slicing.

In the above preparation method, the long-carbon-chain polyamide salt may be a salt obtained by reacting a diamine having 10 to 16 carbon atoms with a diacid having 10 to 18 carbon atoms;

specifically, the long carbon chain polyamide salt may be a polyamide 1010 salt, a polyamide 1011 salt, a polyamide 1012 salt, a polyamide 1014 salt, a polyamide 1111 salt, a polyamide 1211 salt, a polyamide 1212 salt, a polyamide 1214 salt, a polyamide 1313 salt, a polyamide 1311 salt, a polyamide 1312 salt.

In the preparation method, the polyether can be at least one of polyethylene glycol, polypropylene glycol, amino-terminated polyoxyethylene ether, amino-terminated polyoxypropylene ether and polytetrahydrofuran ether glycol, and the relative molecular weight can be 4000-8000;

the polyester can be polycaprolactone diol and/or polycarbonate diol, and the relative molecular weight can be 4000-8000.

In the above preparation method, the anti-ultraviolet agent may be at least one of 2, 4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone, p-octylphenyl salicylate and 4-tert-butylphenyl salicylate; the uvioresistant agent at least contains more than one functional group;

the antioxidant can be antioxidant 1010 and/or antioxidant 1098;

the catalyst may be at least one of tetrabutyl titanate and/or tetrabutyl zirconate.

In the preparation method, all the raw materials are mixed and then uniformly stirred at the stirring speed of 400-1000 rpm.

In the preparation method, the pressure maintaining time is 70-120 min;

the pressure relief time is 40-80 min;

and the vacuum pressure after vacuumizing is 0.05-5 KPa.

In the preparation method, the adding amount of the polyether and/or the polyester is 50-90% of the total weight of the long-carbon-chain polyamide salt and the polyether and/or the polyester.

In the preparation method, the addition amount of the anti-ultraviolet agent is 1-3% of the total weight of the long carbon chain polyamide salt and the polyether and/or polyester.

In the preparation method, the addition amount of the antioxidant is 0.5-1% of the total weight of the long carbon chain polyamide salt and the polyether and/or polyester.

In the preparation method, the addition amount of the catalyst is 0.3-0.5% of the total weight of the long carbon chain polyamide salt and the polyether and/or polyester.

In the above preparation method, the amount of the added water is 20 to 30% of the total weight of the long carbon chain polyamide salt and the polyether and/or polyester, and the water may be deionized water.

The ultraviolet-resistant polyamide elastomer prepared by the method also belongs to the protection scope of the invention;

the anti-ultraviolet polyamide elastomer provided by the invention has excellent anti-ultraviolet performance due to the participation of active functional groups contained in the anti-ultraviolet agent in polymerization reaction, has low cost of preparation raw materials, is harmless to the environment and good in rebound resilience, and can be applied to the fields of high-grade sports equipment, medical materials, special anti-ultraviolet materials and the like.

Detailed Description

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

Examples 1,

Adding 2000g of long carbon chain polyamide 1212 salt, 2000g of polytetrahydrofuran ether glycol with the relative molecular weight of 8000, 40g of 2, 4-dihydroxy benzophenone, 40g of antioxidant 1010, 12g of tetrabutyl titanate and 800g of deionized water into a reaction kettle, uniformly stirring at the stirring speed of 1000 revolutions per minute, heating to 190 ℃, boosting to 1.5MPa, maintaining the pressure for 70min, and heating to 200 ℃; releasing the pressure to normal pressure for 80min, and heating to 260 ℃; vacuumizing, wherein the vacuum pressure is 0.05KPa, and the time is 2 min; and (3) filling nitrogen, opening a lower discharge port, cooling, granulating and drying the melt to obtain the long carbon chain polyamide elastomer with lasting ultraviolet resistance.

Examples 2,

Adding 2000g of long carbon chain polyamide 1012 salt, 18000g of polypropylene glycol with the relative molecular weight of 4000, 600g of 2-hydroxy-4-methoxybenzophenone, 100g of antioxidant 1098, 100g of tetrabutyl zirconate and 6000g of deionized water into a reaction kettle, uniformly stirring at the stirring speed of 400 revolutions per minute, heating to 170 ℃, boosting to 0.9MPa, maintaining the pressure for 120min, and heating to 220 ℃; releasing the pressure to normal pressure for 40min, and heating to 230 ℃; vacuumizing, wherein the vacuum pressure is 5KPa, and the time is 20 min; and (3) filling nitrogen, opening a lower discharge port, cooling, granulating and drying the melt to obtain the long carbon chain polyamide elastomer with lasting ultraviolet resistance.

Examples 3,

Adding 2000g of long carbon chain polyamide 12 salt, 6000g of amino-terminated polyoxypropylene ether with the relative molecular weight of 5000, 2000g of polycarbonate diol with the relative molecular weight of 6000, 100g of 2-hydroxy-4-n-octoxybenzophenone, 100g of salicylic acid-4-tert-butylphenyl ester, 80g of antioxidant 1098, 20g of tetrabutyl titanate, 20g of tetrabutyl zirconate and 2500g of deionized water into a reaction kettle, uniformly stirring at the stirring speed of 600 revolutions per minute, raising the temperature to 180 ℃, raising the pressure to 1.2MPa, maintaining the pressure for 100min, and raising the temperature to 210 ℃; releasing the pressure to normal pressure for 60min, and heating to 250 ℃; vacuumizing, wherein the vacuum pressure is 1KPa, and the time is 10 min; and (3) filling nitrogen, opening a lower discharge port, cooling, granulating and drying the melt to obtain the long carbon chain polyamide elastomer with lasting ultraviolet resistance.

Comparative examples 1,

The preparation was carried out by following the procedure of example 3 except that the anti-ultraviolet agent was not added, and the obtained sample was taken as comparative sample 1.

The anti-ultraviolet polyamide elastomer obtained in the above embodiment is extracted by boiling water, dried, injection-molded into a standard sample strip for testing according to a standard size, and subjected to anti-ultraviolet aging test.

Placing the prepared standard sample strip into an accelerating weather resisting instrument, and testing conditions are as follows: and (3) carrying out a test in a cycle of irradiation for 1 hour and 42 minutes, spraying for 18 minutes and circulation under a 340-nanometer lamp tube at the temperature of 60 ℃, and observing the yellowing resistant time of the plastic.

As can be seen from the data in Table 1, the elastomers prepared according to the invention have high strength, long-lasting UV resistance and good resilience (impact resilience).

TABLE 1 Properties of the samples

Claims

1. A preparation method of an ultraviolet-resistant polyamide elastomer comprises the following steps:

mixing long-carbon-chain polyamide salt, an anti-ultraviolet agent, an antioxidant, a catalyst, water, polyether and/or polycaprolactone diol and/or polycarbonate diol, heating to 170-190 ℃, boosting the pressure to 0.9-1.5 MPa, maintaining the pressure, and raising the pressure to 200-220 ℃; after the pressure is relieved to normal pressure, heating to 230-260 ℃; vacuumizing, filling nitrogen, discharging and slicing to obtain the product;

the uvioresistant agent is at least one of 2, 4-dihydroxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone, p-octyl phenyl salicylate and 4-tert-butyl phenyl salicylate;

the polyether is at least one of polyethylene glycol, polypropylene glycol, amino-terminated polyoxyethylene ether, amino-terminated polyoxypropylene ether and polytetrahydrofuran ether glycol;

the addition amount of the water is 20-30% of the total weight of the long-carbon-chain polyamide salt and the polyether and/or polycaprolactone diol and/or polycarbonate diol.

2. The method of claim 1, wherein: the long-carbon-chain polyamide salt is obtained by reacting diamine with 10-16 carbon atoms and diacid with 10-18 carbon atoms.

3. The production method according to claim 1 or 2, characterized in that: the antioxidant is antioxidant 1010 and/or antioxidant 1098;

the catalyst is tetrabutyl titanate and/or tetrabutyl zirconate.

4. The production method according to claim 1 or 2, characterized in that: the pressure maintaining time is 70-120 min;

the pressure relief time is 40-80 min;

and the vacuum pressure after vacuumizing is 0.05-5 KPa.

5. The production method according to claim 1 or 2, characterized in that: the adding amount of the polyether and/or polycaprolactone diol and/or polycarbonate diol is 50-90% of the total weight of the long-carbon-chain polyamide salt and the polyether and/or polycaprolactone diol and/or polycarbonate diol;

the addition amount of the uvioresistant agent is 1-3% of the total weight of the long-carbon-chain polyamide salt and the polyether and/or polycaprolactone diol and/or polycarbonate diol.

6. The production method according to claim 1 or 2, characterized in that: the addition amount of the antioxidant is 0.5-1% of the total weight of the long-carbon-chain polyamide salt and the polyether and/or polycaprolactone diol and/or polycarbonate diol;

the addition amount of the catalyst is 0.3-0.5% of the total weight of the long-carbon-chain polyamide salt and the polyether and/or polycaprolactone diol and/or polycarbonate diol.

7. A UV resistant polyamide elastomer prepared by the process of any one of claims 1 to 6.